CN106637131A

CN106637131A - Film deposition apparatus using silicon material

Info

Publication number: CN106637131A
Application number: CN201610712432.4A
Authority: CN
Inventors: 奈良井哲; 川上信之; 慈幸范洋
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2015-11-04
Filing date: 2016-08-24
Publication date: 2017-05-10
Also published as: KR20170052490A; TWI657163B; JP2017088916A; TW201716624A; KR101907753B1

Abstract

The invention provides a film forming apparatus using a silicon material, a film layer is formed on substrate that becomes a sample, the film forming device has a reaction chamber having a sample holding mechanism and an exhaust mechanism, and the reaction chamber includes a raw material supply component which mixes a silicon raw material with oxidizing gas; an energy supply component which applies energy so that the silicon raw material is oxidized and a film layer is formed; and an unreacted raw material recovery component which enables an unreacted raw material to be decomposed or adsorbed to a decomposer in the exhaust mechanism. The silicon raw material is an organic compound containing at least one of silicon, oxygen and carbon, so that the volume of supply is adjusted in the way that the total molecule number A of generated full oxide and the atom number B of silicon contained in the silicon raw material satisfy the relation (A-B)/B<=6.75 under the condition that silicon raw material 1 is completely oxidized in a molecular chemometry mode.

Description

Using the film formation device of silicon raw material

Technical field

The present invention relates to a kind of film formation device of use silicon raw material, more particularly to a kind of to form organic electroluminescent The packaging neck of (electroluminescent, EL) illumination, organic el display, the backboard of solar cell, food, pharmaceuticals etc. Obstruct membrane used in Obstruct membrane used in domain etc., or the sealing of electronic component such as organic EL element, solar battery element etc. The film formation device of thin layer.

Background technology

The Obstruct membrane conduct of the thin film of the metals such as the metal-oxides such as aluminium oxide, silicon oxide or aluminum is formed with resin film Prevent the rotten packing technique of the food caused by oxygen etc. or pharmaceuticals etc. and extensively utilize.

In addition, in recent years in person in electronics, organic EL illuminating, organic el display etc. using organic molecule element Exploitation, practical it is in progress.For light weight, the viewpoint of low cost, for being replaced using the Obstruct membrane of resin film base material The demand for utilizing of glass substrate is improved.

But, the Obstruct membrane of resin base material is compared with glass substrate, and water vapor barrier property is very low, and existing to suppress The problem of the deterioration in characteristics of organic molecule element.

In order to solve the problem, the exploitation of the higher film of barrier is being advanced.Such as barrier film of patent documentation 1 Disclose following technology：By using plasma chemical vapor deposition, by the silicon oxide film of carbon containing and gas barrier property coated film Lamination, can form the excellent adhesion of base material film, the silicon oxide film of carbon containing and gas barrier property coated film, and the silicon oxide of the carbon containing The especially excellent barrier film such as flexibility, ductility, bendability of film.

However, gas barrier film as above be exposed to for a long time etc. in the room outside it is harsh under conditions of in the case of, understand in high score Splitting is produced between subtree adipose membrane and the silicon oxide film of carbon containing, the function as barrier film can be undermined, therefore it is required that more High durability.

On the other hand, patent documentation 2 and Patent Document 3 discloses with monolayer obtain high barrier technology.By inciting somebody to action Barrier layer is set to monolayer, is possible with a step to manufacture.

Specifically, Patent Document 2 discloses：By the one or two sides in the polymeric membrane for becoming base material, utilize Chemical vapor deposition (Chemical Vapor Deposition, CVD) method forming silicon oxycarbide films, so as to obtain barrier High gas barrier film.In addition, Patent Document 3 discloses possessing at least one of which thin layer at least unilateral surface of base material Gas barrier multilayer film, by controlling the ratio of the carbon atom in thin layer, and has sufficient gas barrier property, when film can be suppressed to bend Gas barrier property decline.

[prior art literature]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2008-179104 publication

[patent documentation 2] Japanese Patent Laid-Open 2011-42835 publication

[patent documentation 3] Japanese Patent Laid-Open 2012-81630 publication

The content of the invention

[the invention problem to be solved]

In patent documentation 2 and patent documentation 3, though using plasma enhanced chemical vapor deposition method (Plasma Enhanced Chemical Vapor Deposition, PECVD) forming the Obstruct membrane of monolayer, but existing PECVD skills It is difficult to be that of obtaining sufficient film forming speed in art.Although the demand for wanting the film forming speed of raising PECVD is high, exist Various restrictions, are not easy to.

The method for improving the film forming speed mainly considers following two：(1) the input electric power increase of plasma is made Method and (2) make the method that raw material quantity delivered increases.

However, for (1) electric power increase, just by heating cause for the viewpoint of the damage of film base material, deposit Becoming the power value of high limit of tolerance.In addition, for (2) raw material quantity delivered increase, according to the swept volume of pump Balance to determine the upper limit of raw material quantity delivered.That is, the limit of film forming speed is determined according to the composition of film formation device.As film forming The countermeasure of the composition change of device, for the improvement that described (1) considers cooling system, for the increasing that described (2) consider pump quantity If, but these cannot avoid the maximization of film formation device or increasing considerably for film forming cost.

The present invention be in view of the situation and formed, it is therefore intended that a kind of film formation device is provided, film forming dress can not increased In the case of the maximization put or film forming cost, the film forming speed using the thin layer (Obstruct membrane) of PECVD is improved, carried out steady Tailor-made industry.

[means to solve the problem]

The present inventor et al. be repeated effort research, as a result find, by the Obstruct membrane using PECVD into In film, efficiently film forming is carried out using raw material, and reclaim unwanted unreacted raw material, it is possible to resolve the problem, so as to Complete the present invention.

[The effect of invention]

According to the present invention, can be fast to improve the film forming of Obstruct membrane (thin layer) by efficiently carrying out film forming using raw material Degree, can carry out the stable operation of film formation device by reclaiming unwanted unreacted raw material in addition.Can be in not aggrandizement apparatus Maximization or film forming cost in the case of, improve film forming speed, film forming is the Obstruct membrane of the excellent monolayer of barrier.

Description of the drawings

Fig. 1 is the pie graph of that represents representational film formation device.

Fig. 2 is the pie graph of that represents film formation device in the case of heating to gas extraction system pipe arrangement.

Fig. 3 be represent possess the filter that trapped of dust to generating in unreacted raw materials recovery part into The pie graph of of film device.

Fig. 4 be represent possess the filter that trapped of dust to generating in unreacted raw materials recovery part into The pie graph of of film device.

Fig. 5 be represent exhaust gear for vacuum exhaust mechanism and possess oily recirculator (oil recirculator) into The pie graph of of film device.

Fig. 6 be represent silicon raw material be octamethylcy-clotetrasiloxane (octamethylcyclotetrasiloxane, The chart of the measurement result (cooling procedure) of the exhaust mass analysis in the case of OMCTS).

Fig. 7 is the measurement result (regenerative process) for representing the exhaust mass analysis in the case where silicon raw material is OMCTS Chart.

Description of reference numerals：

1：Reative cell

2：Energy supply part

3：Raw material supply part

4、5：Pipe arrangement

4a、5a：Automatic valve

10：Pressure adjustment unit part

11：Pirani ga(u)ge

12、13：Capacitance manometer

14：Baroswitch

15：Cold cathode is advised

20：Exhaust gear

21：Turbomolecular pump

22、22A：Oil rotation pump

23：Dry pump

24：Cold-trap

25：Gate valve

26：Leak valve

27：Effusion meter

30：Filter

40：Oily recirculator

Specific embodiment

The film formation device of the present invention is the film formation device that thin layer is formed on the base material for become sample, wherein：

With reative cell, the reative cell possesses：Load the sample maintaining body of the sample and comprising gas extraction system The exhaust gear of pipe arrangement,

The reative cell includes：Raw material supply part, in the vicinity of the placed sample thin layer will be become The silicon raw material of raw material mix with oxidizing gas；

Energy supply part, the silicon raw material and the oxidizing gas to being supplied applies energy, using the oxygen The property changed gas aoxidizes the silicon raw material and forms thin layer；And

Unreacted raw materials recovery part, makes not supply the unreacted raw material to the oxidation in the exhaust gear Decompose or be adsorbed on analyte；And

The silicon raw material is at least one organic compound containing silicon, oxygen and carbon,

In energy supply step, with the institute in the case of by the molecular chemistry Targets ground complete oxidation of the silicon raw material 1 The aggregated molecule number A of the total oxygen compound of generation meets (A-B)/B≤6.75 with atomic number B of silicon contained in the silicon raw material The mode of relation, adjusts at least quantity delivered of any one of the silicon raw material and the oxidizing gas.

Generally chemical reaction has following mechanism：In the case where reaction kind A and B is raw material, the molecule of A (or B) is obtained Certain energy and become unstable, in order to become it is more stable and with B (or A) bonds, become stable on energy and generate product C.In order that raw material A (or B) is activated and needs activation evergy Δ E.Carry out with raw material B (or A) in the raw material A (or B) more than Δ E React and in the case of generation product C, constitute generic key of the raw material A with total bond energy of the element of raw material B more than composition product C The situation of knot energy becomes exothermic reaction, and its contrary situation becomes the endothermic reaction.Many exothermic reactions fast using response speed.

In the present invention, in order to generate the Obstruct membrane of such as web-like film as thin layer, it is desirable to obtain quick response speed. Therefore, in the case where silicon dioxide film is generated, using using oxygen the reaction that the Organic Ingredientss with silicon are aoxidized is made.Separately Outward, in the reaction example, product is only C, but industrially in addition to product C, generally also reaction of formation by-product D.

Therefore, the result that the present inventor et al. carries out making great efforts research is, successfully by raw material A with raw material B effectively giving birth to Into product C, and find the element group of most suitable silicon raw material for the generation of byproduct of reaction D is suppressed to into Min. Into than.In addition, have also discovered the part of more quickly the generated byproduct of reaction D of removal.

System of selection to detailed raw material below is illustrated.

Silicon raw material in the present invention is the organic compound containing silicon, oxygen and carbon, can be a kind of organic compound, alternatively The mixture of two or more organic compound.

For the aspect of low environmental load, preferably comprising the compound with circulus as silicon raw material.In addition, Even if being not circulus, as long as organic functional base contained in molecule is few, then it is possible with.Specifically, preferably Comprising monomethylsilane and dimethylsilane at least any one.Additionally, with regard to carrying capacity of environment, described later<Oxidisability gas Body>Middle detailed description.

Compound with circulus is more preferably comprising cyclic siloxane compound and cyclic oxosilane compound At least any one, especially preferred cyclic siloxane compound can enumerate octamethylcy-clotetrasiloxane, tetramethyl cyclotetrasiloxane silica Alkane, hexamethyl cyclotrisiloxane etc., wherein and then more preferably octamethylcy-clotetrasiloxane, tetramethyl-ring tetrasiloxane.In addition, Especially preferred cyclic oxosilane compound can enumerate silazane of 2,2,4,4,6,6- pregnancy basic ring three etc..

These compounds only comprising one kind can be included also two or more.

In addition, in silicon raw material, it is complete with what is generated in the case of by the molecular chemistry Targets ground complete oxidation of silicon raw material 1 The aggregated molecule number A of oxide meets the side of the relation of (A-B)/B≤6.75 with silicon atom number B contained in the silicon raw material Formula, adjusts at least quantity delivered of any one of silicon raw material and oxidizing gas.

The oxide generated in the case of by silicon raw material stoichiometry ground complete oxidation depends on the silicon raw material In contained atom kind, but mainly set SiO₂、CO₂、H₂O、N₂O.These molecular number it is total equivalent to molecular number A.In addition, Silicon atom number B is equivalent to the SiO₂Molecular number.

That is, there is SiO in (A-B) in so-called relational expression (A-B)/B₂、CO₂、H₂O and N₂O these four as oxide In the case of, equivalent to CO₂、H₂O and N₂The molecular number of O it is total.Additionally, these oxides in reaction environment as gas Body and generate.

According to the above, so-called relational expression (A-B)/B is equivalent to the SiO for generating 1 molecule₂When produced gas molecule it is total Amount.Therefore, relational expression (A-B)/B is contemplated that to generate the SiO of 1 molecule₂When required exhaust loads index.

For the viewpoint that exhaust loads are reduced, (A-B)/B is preferably less, substantially must go out from the viewpoint of practicality Send selected its scope.In the present invention, as the benchmark, in order that exhaust loads are less than patent documentation 2 and patent documentation 3 Hexamethyl disiloxane (hexamethyldisiloxane, HMDSO) (O [Si (CH disclosed in embodiment₃)₃]₂), (A-B)/B It is set to less than 6.75.Additionally, the raw material being also shown in the scope of the claim of patent documentation 2 beyond HMDSO, but as real That what is applied example and illustrate is only HMDSO.

The chemical equation such as following formula (1) for making HMDSO carry out in the case of oxidation reaction is described.

O[Si(CH₃)₃]₂+10.5O₂→2SiO₂+6CO₂+9H₂O formulas (1)

Now, the value of the A in the relational expression is 2 for the value of 17, B, therefore obtains (A-B)/B=7.5.

As described above, be in the present invention so that exhaust loads are less than for the purpose of HMDSO, if but (A-B)/B is less than 6.75, Then more than 10% can be reduced in terms of HMDSO ratios.(A-B) value of/B is more preferably less than 6.5, especially preferably less than 6.

In the film formation device of the present invention, energy is applied to silicon raw material and oxidizing gas, made using the oxidizing gas The silicon raw material is aoxidized and forms thin layer (Obstruct membrane).

In the oxidation reaction using oxidizing gas, the amount of the oxidizing gas being preferably fed in reaction vessel It is controlled to appropriate scope.As the amount of the oxidizing gas for being supplied, it is believed that simply by the presence of for by silicon raw material stoichiometry Property ground complete oxidation for sufficient amount.In addition, be one of for purposes of the present invention the stable operation of device, preferably Exhaust loads are strongly reduced, therefore preferably supply is also strongly few to the oxidizing gas in reaction vessel.

According to the above, for the aspect that exhaust loads are reduced, the quantity delivered of oxidizing gas preferably no more than in order to The required amount by silicon raw material stoichiometry ground complete oxidation.Additionally, it is preferred that to possess controlling organization, it is used to make oxidisability The quantity delivered of gas is not over for the required amount by silicon raw material stoichiometry ground complete oxidation.

In addition, for the aspect that exhaust loads are reduced, by the shape of thin layer of the oxidation reaction of silicon raw material to carry out Into the reacted of the utilization oxidizing gas for being preferably only silicon raw material.Oxidizing gas can enumerate oxygen, ozone, water Steam etc., wherein for the aspect of operational ease, preferably oxygen.

In addition, the formation of the thin layer is in addition to silicon raw material and oxidizing gas, also can be further in rare gas In the presence of carry out.

Rare gas can enumerate He, Ne, Ar, Xe etc., wherein Ar due to less expensive and easy acquisition it is preferred that.

It is so-called in order to by silicon raw material stoichiometry ground complete oxidation and required oxidizing gas quantity delivered, for example exist It is as understood according to the formula (1), relative to every 1 molecule in the case that silicon raw material is HMDSO and oxidizing gas are oxygen HMDSO and be the oxygen of 10.5 molecules.That is, as long as the amount of the oxygen supplied to reaction vessel is controlled to relative to the 1 of HMDSO 10.5 left and right.

Then, with regard to the exhaust loads of various silicon raw materials, will be shown in Table 1 obtained by the value of estimation relational expression (A-B)/B.

[table 1]

	SiO₂Generate	CO₂Generate	H₂O is generated	NO₂Generate	A-B	(A-B)/B
							HMDSO	2	6	9		15	7.5
OMCTS	4	8	12		20	5
							TMCTS	4	4	6		10	2.5
HMCT siloxanes	3	6	9		15	5
							HMCT silazane	3	6	10.5	3	19.5	6.5
Monomethylsilane	1	1	3		4	4
							Dimethylsilane	1	2	4		6	6
TEOS	1	8	10		18	18
							Single silane	1	0	2		2	2

Additionally, " HMDSO " refers to hexamethyl disiloxane in this specification, " OMCTS " refers to octamethylcy-clotetrasiloxane, " TMCTS " refers to tetramethyl-ring tetrasiloxane, and " HMCT siloxanes (HMCT Siloxane) " refers to hexamethyl cyclotrisiloxane, " HMCT silazane (HMCT Silazane) " refers to the silazane of 2,2,4,4,6,6- pregnancy basic ring three, and " TEOS " refers to four ethoxies Base silane.

Can be confirmed according to table 1, OMCTS, TMCTS, HMCT siloxanes (HMCT Siloxane), HMCT silazane (HMCT Silazane), monomethylsilane and dimethylsilane are compared with HMDSO ((A-B)/B=7.5), and exhaust loads are low.Additionally, making Value for the exhaust loads ((A-B)/B) of the TEOS of widely used organosilicone compounds is 18, is shown compared with HMDSO The very high exhaust loads of speech.

In addition, as reference, illustrating that using CVD the aerofluxuss to form widely used single silane during silicon oxide film are born Lotus.Single silane shows minimum exhaust loads ((A-B)/B=2), but single silicon in the silicon raw material compound shown in the table 1 Do not include carbon atom in alkane, so be difficult to directly be utilized as the membranaceous Obstruct membrane purposes of resin.

The film formation device of the present invention has reative cell, and the reative cell possesses：Mounting becomes the sample of the base material of sample and protects Mechanism and the exhaust gear comprising gas extraction system pipe arrangement are held, the reative cell includes：Raw material supply part, placed The vicinity of the sample mixes the silicon raw material for becoming the raw material of the thin layer with oxidizing gas；Energy supply part, it is right The silicon raw material for being supplied applies energy with the oxidizing gas, and using the oxidizing gas silicon raw material is aoxidized And form thin layer；And unreacted raw materials recovery part, make not supply the unreacted raw material to the oxidation described Decompose in exhaust gear or be adsorbed on analyte.

(energy supply part)

The present inventor et al. aoxidizes the silicon raw material by selecting silicon raw material as described, can quickly react speed Degree, and can be using as the CO of byproduct of reaction synthesizing the thin layer (silicon dioxide film, Obstruct membrane) as product₂、H₂O、N₂O Deng generation be set to Min..

In order to cause the oxidation reaction, as the energy for applying more than activation evergy Δ E to silicon raw material and oxidizing gas The energy supply step of amount, for example, can preferably enumerate and be reacted in a vacuum and using the PECVD of plasma.It is described PECVD due to reducing exhaust loads and use more cheap vacuum pump, so industrially effective.

Also preferably together with PECVD, or using CVD (the Chemical Vapor using thermal energy Deposition, chemical vapour deposition technique) or replace PECVD using the optical cvd method of light energy.

Even if in addition, in the case where being applied to not use the device of vacuum, can also simplify gas extraction system and can simplify anti- The processing meanss of by-product are answered, so it is preferred that.

Additionally, the span of control of composition control can be expanded and for the aspect of the more excellent material of formation characteristic, it is more excellent Elect the energy in energy supply part as and with selected from least two in plasma, heat and the group that constituted of light.That is, More preferably and with least two methods in the group constituted selected from PECVD, CVD and optical cvd method.

(unreacted raw materials recovery part)

In the film formation device of the present invention, raw material (silicon raw material and the oxidisability reacted near the base material for becoming sample Gas) product (thin layer) is generated on the substrate.Due to the response speed of the raw material it is quick, so in order to be come with high speed Film forming is thin layer, and the feed speed of raw material also must be fast.If accelerating feed speed, the oxidation not supplied to silicon raw material is produced The unreacted raw material (unreacted silicon raw material and unreacted oxidizing gas) of reaction.If in addition, starting near base material Raw material (raw material that the material concentration declines) long-time of reaction is stopped, then cause the decline of response speed.

Therefore, it is necessary to by under the unreacting material (unreacted oxidizing gas) or material concentration near base material The raw material of drop is expelled in gas extraction system.Therefore, film formation device of the invention includes unreacted raw materials recovery part, it is described not The raw materials recovery part of reaction makes the unreacted raw material decompose or inhale in the exhaust gear comprising gas extraction system pipe arrangement Attached decomposed analyte.

The reason for unreacted raw materials recovery part becomes required is as described below.

The unreacting material becomes silicon dioxide and becomes membranaceous attachment in gas extraction system, or generates powdery Silicon dioxide powder, therefore exist make aerofluxuss with blockage misgivings.In addition, pile up in gas extraction system having silicon dioxide powder In the case of, need the cleaning operation to remove the silicon dioxide powder.Further, using vacuum pumping system as exhaust system In the case of system, because piling up as generation on the movable vane piece of turbomolecular pump (turbo-molecular pump) and stator blade Silicon dioxide powder of reactant etc., and decline exhaust performance, or silicon dioxide powder piles with movable vane piece or stator blade and becomes and draw The reason for playing failure.As donkey pump come use oil rotation pump (oil rotary pump) or dry pump (dry pump) in, Silicon dioxide powder is piled up on pump, making the frictional force of hermetic unit or machinery increases and become the reason for causing failure.

According to the above, using at a high speed and efficient film forming is as in the film formation device of purpose, it is necessary to including unreacted original Material recovery part, the unreacted raw materials recovery part makes unreacted raw material decompose in exhaust gear or adsorb to divide The analyte of solution.Additionally, in unreacted raw materials recovery part, unreacted raw material is not only reclaimed, product in the middle of course of reaction Thing or byproduct of reaction are also recovered in the lump.

As unreacted raw materials recovery part, it is preferable to use cool down waste gas and adsorb the cold of unreacted raw material Trap.

So-called cold-trap, is to cool down the waste gas for being caught and concentrate the device for liquid or solid, specifically, in pipe arrangement The interior part with reduction wall surface temperature.The unreacted raw material or course of reaction intermediate product and byproduct of reaction (with It is adsorbed on the wall of gas extraction system pipe arrangement down sometimes referred to simply as " unreacted raw material etc. ").The relation of the absorption is in theory On represented by the adsorption isotherm of Langmuir (Langmuir), be by cloth Shandong in the case where adsorption layer is related to several molecules The adsorption-type of Nuo-Ai Meite-Teller (Brunauer-Emmett-Teller, BET) is representing.In any one adsorption-type, Lower for wall surface temperature, the molecule for being adsorbed is more, and unreacted raw material etc. is comparatively reclaimed from gas extraction system pipe arrangement Efficiency becomes good.

The cryogen that cryogen used in cold-trap can be usually used using liquid nitrogen, liquid helium, fluorine system coolant etc..

Additionally, it is preferred that being the time of staying for being set to S words etc. to extend in cold-trap by the gas extraction system pipe arrangement in cold-trap.

If in addition, while using cold-trap, improving the wall of the gas extraction system pipe arrangement that reative cell side is more located at compared with cold-trap Temperature, then according to the relation of the adsorption-type, molecule is more optionally adsorbed in cold-trap.Therefore, more preferably to the row At least a portion of gas system pipe arrangement is heated.

Also cold-trap can not be used to be used as unreacted raw materials recovery part, but arranging in exhaust gear makes unreacted The impurity recovering mechanism of mode that burns again such as raw material.For example preferably with using plasma by unreacted raw material point The plasma type purifier (plasma type detoxifying device) of solution is used as unreacted raw materials recovery Part.

If in addition, possibility, also can be passed through waste gas and reclaim not in the reaction material of the reaction material of solid or liquid Raw material of reaction etc..

Exhaust gear in unreacted raw materials recovery part is preferably vacuum exhaust mechanism, generally using turbomolecular pump Carry out aerofluxuss.During using turbomolecular pump, the donkey pump such as rotary pump or dry pump also can be used in the lump.

In the case of using cold-trap, the exhaust side preferably in the turbomolecular pump arranges cold-trap, and compared with cold-trap For more by exhaust side configure donkey pump.

Additionally, in the case of using the cryopump (cryo pump) with cold-trap effect, cryopump shows cold-trap Effect, but due to for accumulation formula pump, so adsorbed molecule continually must be reclaimed by Regeneration Treatment, under production efficiency Drop.

In the case of using rotary pump as donkey pump, and preferably possessing makes the oil circulation removal of vacuum of rotary pump solid The oily recirculator of body composition.That is, the solid constituents such as unreacted raw material are absorbed in the vacuum oil for preferably making circulation, using oil Recirculator is reclaiming the solid constituent.Now, it is contained not anti-in can passing through to arrange filter to remove the vacuum oil The impurity such as the raw material answered, it is possible to use electrostatic impurity recovering mechanism.

In unreacted raw materials recovery part, preferably also possess to the decomposition because of unreacted raw material or institute The filter that the absorption of the analyte of decomposition and the dust (silicon dioxide powder etc.) that generates are trapped.Filter may be disposed at cold Between the upstream side of trap or cold-trap and dry pump etc..If compared with cold-trap further downstream (between cold-trap and dry pump) arrange filter, The dust thoroughly not reclaimed by unreacted raw materials recovery part (cold-trap), the recovery of dust can be reclaimed using the filter Efficiency rises.

(raw material supply part)

In raw material supply part, in the vicinity of the base material for becoming sample silicon raw material and the oxidation of the raw material of thin layer will be become Property gas mixing.

In the case where such as OMCTS is used as silicon raw material, OMCTS have it is activated after willing characteristic. Therefore, it is the material favourable for high speed film forming, while with the one side with oxidizing gas immediate response.That is, OMCTS and oxygen Change property gas raw material from obtain activation evergy after until arrival substrate surface till in a period of reacted, it is impossible in base Thin layer is formed on plate.Further, the material concentration near base material is also reduced and declines film forming speed.

In order that raw material is reacted near base material and thin layer is efficiently formed on base material, obtain from silicon raw material The position that the position of activation evergy obtains activation evergy with oxidizing gas is risen and equidistantly configures base material, is carried out at a high speed and uniform Process.Therefore, in base material in the case of large-scale, silicon raw material and oxidisability gas are not preferably supplied from same blow-off outlet Body, but via the unstrpped gas supply part with the unstrpped gas blow-off outlet of more than 2, the base feed on base material.

With regard to the feed speed of silicon raw material, as gas, preferably 1sccm～750sccm, more preferably 10sccm～ 400sccm.As liquid, more preferably preferably 0.01g/min～10g/min, 0.1g/min～5g/min.

The feed speed of oxidizing gas is preferably 10sccm～10000sccm, and more preferably 100sccm～ 5000sccm。

In the case where the oxidation reaction of silicon raw material is further caused in the presence of rare gas, the supply speed of rare gas Degree is preferably 5sccm～750sccm, more preferably 5sccm～400sccm.

(film formation device composition)

The representative composition of the film formation device of the present invention is shown in Fig. 1～Fig. 5, but the composition of the film formation device of the present invention These compositions are not limited to, can arbitrarily be deformed and implement in the range of without departing from idea of the invention.

In Fig. 1, the sample maintaining body (not shown) of storage mounting sample in reative cell 1, and keep with the sample Mechanism to and configuration energy supply part 2.The sample maintaining body can possess heater, sample can be carried out in film forming Heating.And, from energy supply part 2 to energy such as sample supply plasma, light or the heat being held on sample maintaining body Amount.The energy also can simultaneously with two or more.

Raw material supply part 3 is connected with reative cell 1.In raw material supply part 3, by from silicon raw material accumulator tank Pipe arrangement 4 supplying the silicon raw materials such as OMCTS, and by supplying the oxygen such as such as oxygen from the pipe arrangement 5 of oxidizing gas accumulator tank The property changed gas.And, to meet relational expression (A-B)/B≤6.75 mentioned above in the way of, using automatic valve 4a, automatic valve 5a To control each flow of silicon raw material and oxidizing gas.

In addition, being connected with pressure adjustment unit part 10 on reative cell 1.Pressure adjustment unit part 10 includes such as Pi Lani vacuum Meter (Pirani vacuum gauge) 11, capacitance manometer (capacitance manometer) 12, capacitance manometer 13, gas Compress switch 14, respectively by valve operation to control film forming before reative cell 1 vacuum state.In addition, being connected with reative cell 1 Cold cathode advises (cold cathode gauge) 15, determines intrinsic pressure in film forming.

Further, exhaust gear 20 is connected with reative cell 1, in film forming, is will be present in unreacted near sample Silicon raw material gas or oxidizing gas are discharged.Aerofluxuss are carried out by turbomolecular pump 21, but also can simultaneously with oil rotation pump (rotation Pump) 22 or dry pump 23.Attachment, accumulation reaction of formation thing (such as titanium dioxide on the movable vane piece or stator blade of turbomolecular pump 21 Silica flour) etc. and decline exhaust performance, or the reason for become the failure for causing pump, therefore in the present invention, in turbomolecular pump 21 Back segment set up cold-trap 24.In addition, cold-trap 24 is also connected to prevent product in the oil rotation with oil rotation pump 22 and dry pump 23 Attachment, accumulation in pump 22, dry pump 23.

In addition, between turbomolecular pump 21 and reative cell 1, being situated between every gate valve 25 is provided with, by leak valve 26, using stream Gauge 27 is determining exhausted air quantity.

Additionally, the device or equipment, pipe arrangement that constitute exhaust gear 20 are replaced by the nitrogen from nitrogen line.

Additionally, the wall surface temperature by improving the pipe arrangement that reative cell side is more located at compared with cold-trap 24, can make unreacted raw material More optionally it is adsorbed on cold-trap 24.Therefore, also can be as shown in the double dot dash line of Fig. 2, between reative cell 1 and cold-trap 24 Some or all of gas extraction system pipe arrangement is heated.

In addition, the dust in order to trap product, also can as shown in Figure 3 in the upstream side of cold-trap 24 or as shown in Figure 4 Between cold-trap 24 and dry pump 23, it is situated between every installation filter 30.Though additionally, omit diagram, also can the upstream side of cold-trap 24, And both the upper setting filters 30 between cold-trap 24 and dry pump 23.

Additionally, in described each film formation device, using oil rotation pump 22 and dry pump 23 as donkey pump, but also can be such as Fig. 5 It is shown, replace dry pump 23 using oil rotation pump 22A.Now, oily recirculator 40 is set up, makes the vacuum of oil rotation pump 22A oil circulation And remove solid constituent.Thus, filter 30 as shown in Figure 3, Figure 4 can also be omitted.

[embodiment]

Hereinafter, embodiment is enumerated, more specific description, but the present invention is carried out to the present invention not by these embodiment limits System, also can be suitable for applying change in the range of described or aftermentioned purport to implement, and these are both contained in the present invention's In technical scope.

[test example]

Using the film formation device shown in Fig. 1, and made as silicon raw material using OMCTS (embodiment) or HMDSO (comparative example) With oxygen as oxidizing gas, silicon thin film is formed on base material.Base material is 4 English for using the manufacture of Sha Muke (Samco) company Very little (100) single-crystal wafer (single crystal wafer).By membrance casting condition and the details of the equipment for constituting film formation device It is shown in following.Additionally, the reaction equation of the complete oxidation of setting OMCTS and HMDSO is shown in following.

[Si(CH₃)₂O]₄+16O₂→4SiO₂+8CO₂+12H₂O

O[Si(CH₃)₃]₂+12O₂→2SiO₂+6CO₂+9H₂O

(membrance casting condition)

Film formation device：Inductively coupled plasma (Inductively Coupled Plasma, ICP) formula plasma CVD device

Radio frequency (Radio Frequency, RF) puts into electric power：300W

Pedestal (susceptor) temperature：60℃

. pressure：4Pa

Silicon raw material quantity delivered：The HMDSO of the OMCTS/10sccm of 10sccm

Oxidizing gas quantity delivered (oxygen)：100sccm

(device is constituted：ICP formula plasma CVD equipments)

Bias applying power supply

Bias RF (is manufactured, MFG-20SA) with RF power supplys up to friendship perseverance (DAIHEN)

380-400kHz variable power supplies

Substrate bias apply to use

Peak power output is 2kW

Bias RF matching box controllers (matching BOX controller) are (up to friendship perseverance (DAIHEN) manufacture, MFM- 20SA)

Matching box/controller

ICP produces mechanism

Dielectric window

φ 142mm quartz windows (window peristome is φ 114mm)

Material thickness t=8.8mm

ICP produces mechanism's antenna

φ100mm

The antennas of volume 2

φ 6mm coppers

Device

Reaction chamber (Si Puli (SPLEAD) is manufactured, square standard chamber)

Internal diameter φ 270mm

Height 422mm

Sample bench (manufacture of slope mouth electric heating)

External diameter φ 154mm

4 inches of φ can be carried

Substrate heats 150 DEG C of highest

The distance of dielectric window to sample bench is 160mm

The distance of gas introduction port to sample bench is 80mm

Gas distributor (gas distributor)

φ250mm

8 grades match somebody with somebody feed point

Gate valve (VAT is manufactured, 64248-JE52-0100)

VF250 flanges

Nominal diameter is 250mm

Turbo-molecular pump intake carries automatic pallet-changing device (automatic pallet changer, APC) function (VAT is manufactured, self-adaptive pressure controller (ADAPTIVE PRESSURE CONTROLLER) PM-5)

Controller/automatic pressure control device

Turbomolecular pump (Shimadzu Seisakusho Ltd. manufactures, TMP-1003LMC)

VG200 nominal diameters connect for the flange of 200mm

Capacity is 1080L/sec (@nitrogen) chemical specification

Dry pump (Mitsubishi Heavy Industries Ltd manufacture, DP-500)

Capacity 500L/min

(device is constituted：Cold-trap)

Inner core

Using the rustless steel steel (SUS304) of 18Cr-8Ni, internal diameter will be made：The end of the inner core of 100mm (material thickness=3mm) Face welding and the person of being sealed to form are fused to the flange of JIS200mm, and it is identical to output with inner core peristome in the central authorities of the flange The hole of diameter, can import liquid from outside.The SUS304 barriers of 4 semicircles of side welding outer tube.Inner core is highly set to 350mm。

Outer tube

Using SUS304, internal diameter is sealed for the cylinder end welding of 200mm (material thickness t=3mm).In peristome welding JIS200mm flanges are internally formed space receiving inner core in container.

Gas introduction port and outlet are set to KF25 flanges, and outer tube is highly set to 360mm.

Using method

The liquid nitrogen of about 500mL is imported inside the cold-trap of the acquisition, leading from the upside of cold-trap import in mouth waste gas.By Then semicircle barrier, so discharge when waste gas draws S in cold-trap.

(thin layer)

For the thin layer of the silicon dioxide of the acquisition, the film thickness measuring dress manufactured using resistance to promise (Nanometrics) Put (pattern：M5100A) determining, analyze.

Its result is, the use of OMCTS as the film forming speed in the case of silicon raw material is 250nm/min, the inch wafers of φ 4 Film thickness distribution in face is calculated as 19% with minimax (max-min) method.

In addition, the use of HMDSO as the film forming speed in the case of silicon raw material is 134nm/min, in the inch wafer faces of φ 4 Film thickness distribution be calculated as 16% with minimax (max-min methods).

(waste gas)

The quadrupole quality analysis apparatus of excellent Bake (ULVAC) company are set on the gas extraction system pipe arrangement of cold-trap outlet (QMASS：BGM202 sensors), the waste gas discharged during to silica membrane film forming using OMCTS carries out quality analysiss.

Gas flow is to implement to determine under the following conditions.

Oxygen：100sccm

Nitrogen：10sccm

OMCTS：0.1g/min

The nitrogen be as to make the i.e. OMCTS of liquid charging stock gasify vector gas and import.Additionally, in gas extraction system In pipe arrangement, in addition to described, also import to protect the bearing portion of turbomolecular pump not by reactant gas affected it is micro- Amount nitrogen.

Measure is to produce plasma to be set to 300W to implement with the output of RF power supplys (13.56MHz).Gas is led The vacuum of the reaction vessel before entering is 9.5 × 10^-5Pa。

Quadrupole quality analysis apparatus are connected via aperture (orifice) with the pipe arrangement of cold-trap outlet, a part for waste gas In being fed to quadrupole quality analysis apparatus, in the way of maintaining to determine necessary vacuum while carrying out METHOD FOR CONTINUOUS DETERMINATION It is adjusted.Stagnation pressure during measure is 5 × 10^-4Pa～1 × 10^-4The scope of Pa.

Measure is to implement 50 milliseconds to 1 mass.According to the presence or absence of plasma mass number change atom be 2,12, 14、16、18、32、44.This is respectively equivalent to H₂、C、N、O、H₂O、O₂、CO₂Mass number.Though confirm to measurable highest Mass number is 200, but advantageous difference cannot be observed under other mass numbers.In addition, the molecular weight of OMCTS is 296.62, Beyond the measurement range of quadrupole quality analysis apparatus, therefore do not observe.Carry out 7 mass numbers per 350 milliseconds under the described conditions Measure.

The ionizing voltage of quadrupole quality analysis apparatus is 50V, the measure of partial pressure be relative to setting ion current 1 × 10^-7A and be scaled 1 × 10^-5Pa。

The measurement result that exhaust mass is analyzed is shown in Figure 6.

The rising of the partial pressure seen per 500 seconds from determining and starting is by caused by the importing of unstrpped gas, in unstripped gas The value of C slowly declines after temporarily rising after body just importing.Consider that its reason is：The OMCTS of unstrpped gas is imported into oxygen To analysis within the chamber, using the ionizing electron beam of quadrupole quality analysis apparatus, OMCTS enters explosively with the reaction of oxygen OK.Think after fulminant reaction, gently to start the inflow velocity and the exhaust velocity of product for obtaining OMCTS and oxygen Balance, measured value stabilisation.The tendency is in H₂、H₂O and CO₂In, it is also observed that confirming OMCTS to be reacted and being generated Decomposition by-products.

In addition, O and O₂Not it was observed that the tendency, is interpreted as giving enough oxygen in stoichiometry.N₂Also it is same Sample, but think due to being micro, so have neither part nor lot in observable scope in the analysis from the thin film being piled up on sample anti- Should.

Plasma is produced near 800 seconds after gas is imported.By the generation of plasma, H₂、C、H₂O and CO₂Point Pressure rises, O and O₂Partial pressure decline.Think that it is the reaction of the OMCTS and oxygen aided in by the plasma in reaction vessel Situation about causing.Now N₂Partial pressure substantially do not change.

The state for producing plasma is kept after certain hour, liquid nitrogen to be imported in cold-trap near 1200 seconds. Import initially, because liquid nitrogen tails off with evaporation, so add in good time to maintain liquid nitrogen quantity.Import from liquid nitrogen Shi Qi, H₂O and CO₂Partial pressure slowly decline.In addition, though pettiness, but the partial pressure of C also declines.H₂O and CO₂Partial pressure decline it is slow It is the reason for slow：Due to CO₂Condensing temperature it is low, so low temperature is reached inside cold-trap needs the time.

Confirmed, contained C, H in the analyte or byproduct of reaction of OMCTS according to the observation₂O and CO₂Returned by cold-trap Receive.

The partial pressure change of the molecule reclaimed by cold-trap, atom is shown in Table 2.

[table 2]

Then, near 1700 seconds after cold-trap cooling, termination, O and O are produced with plasma is made₂Partial pressure rise, H₂And the partial pressure of C declines, but H₂O and CO₂Partial pressure do not change.This represents the H that plasma is generated when producing₂O and CO₂By cold Trap is all reclaimed.In this process, N₂Partial pressure be not widely varied yet.

Then, the quality analysiss of the process (regenerative process) heated using room temperature after liquid nitrogen will be taken out from cold-trap As a result it is shown in Figure 7.It is now following state：Non- base feed gas, only flows for protection turbine point in waste gas system The purpose of the bearing of sub- pump and the nitrogen that flows.O₂Partial pressure reached below determination limit, H₂And H₂The partial pressure of O also with gas Body is equal partial pressure before importing, unchanged.

From near 4300 seconds, C, CO₂And the partial pressure of O rises.The pattern dependant that partial pressure rises (regenerated in heating process Journey) cold-trap temperature change.Now think：Due to not producing plasma, so the C and O on atom by comprising these Byproduct of reaction that cold-trap is captured or unreacting substance by the ionizing electron beam of quadrupole quality analysis apparatus from Sonization, so as to be detected.Now think：Though it is unconfirmed to significant H₂Increase, but due to the oxygen that there is atom shape, so As H₂O and be detected, or byproduct of reaction or the hydrogen content in unreacting substance it is few and be hidden into H₂Background in.

Therefore, according to the measure unreacting substance or byproduct of reaction from OMCTS can be confirmed by cold trapping.

Additionally, be not provided with cold-trap and in the case of carrying out same measure, in the running between 1 hour or so the row of confirming The vacuum capacity of the dry pump of gas system declines, but in the case where cold-trap is provided with, even if the duration of runs was through more than 10 hours, Failure is not seen yet.

Claims

1. a kind of film formation device, it forms thin layer on the base material for become sample, and the film formation device is characterised by：

With reative cell, the reative cell possesses：Load the sample maintaining body of the sample and comprising gas extraction system pipe arrangement Exhaust gear,

The reative cell includes：Raw material supply part, the original of the thin layer will be become in the vicinity of the placed sample The silicon raw material of material mixes with oxidizing gas；

Energy supply part, the silicon raw material and the oxidizing gas to being supplied applies energy, using the oxidisability Gas aoxidizes the silicon raw material and forms thin layer；And

Unreacted raw materials recovery part, makes not supplying to the unreacted raw material of the oxidation and decomposes in the exhaust gear Or be adsorbed on analyte；And

In energy supply step, to be generated in the case of by the molecular chemistry Targets ground complete oxidation of the silicon raw material 1 Atomic number B of aggregated molecule number A and silicon contained in the silicon raw material of total oxygen compound meet the relation of (A-B)/B≤6.75 Mode, adjust at least quantity delivered of any one of the silicon raw material and the oxidizing gas.

2. film formation device according to claim 1, it is characterised in that：The unreacted raw materials recovery part is by waste gas Cool down and the cold-trap of the unreacted raw material of absorption.

3. film formation device according to claim 2, it is characterised in that：The cold-trap is more located at described in reative cell side At least a portion of gas extraction system pipe arrangement is heated.

4. film formation device according to claim 1, it is characterised in that：The unreacted raw materials recovery part is to utilize Gas ions, by the plasma type purifier of the unreacted raw material decomposes.

5. film formation device according to claim 1, it is characterised in that：Possess filter, the filter to because it is described not The decomposition of described unreacted raw material or the absorption on analyte in the raw materials recovery part of reaction and the dust that generates Trapped.

6. film formation device according to claim 1, it is characterised in that：The exhaust gear is vacuum exhaust mechanism.

7. film formation device according to claim 6, it is characterised in that：The vacuum exhaust mechanism possesses oily recirculator, The oily recirculator makes the vacuum of rotary pump oil circulation and removes solid constituent.

8. film formation device according to claim 1, it is characterised in that：The energy supply step is plasma enhancing Learn vapour deposition process.

9. film formation device according to claim 1, it is characterised in that：The energy supply step is chemical vapor deposition Method.

10. film formation device according to any one of claim 1 to 7, it is characterised in that：The energy supply step is light Chemical vapour deposition technique.

11. film formation devices according to claim 1, it is characterised in that：Energy in the energy supply part and with choosing At least two energy in the group that free plasma, heat and light are constituted.

12. film formation devices according to claim 1, it is characterised in that：The silicon raw material includes the change with circulus Compound.

13. film formation devices according to claim 12, it is characterised in that：The compound with circulus is ring-type Silicone compounds and cyclic oxosilane compound at least any one.

14. film formation devices according to claim 13, it is characterised in that：The cyclic siloxane compound is selected from eight At least oneization in the group that methyl cyclotetrasiloxane, tetramethyl-ring tetrasiloxane and hexamethyl cyclotrisiloxane are constituted Compound.

15. film formation devices according to claim 13, it is characterised in that：The cyclic oxosilane compound is 2,2,4,4, The silazane of 6,6- pregnancy basic ring three.

16. film formation devices according to claim 1, it is characterised in that：The silicon raw material includes monomethylsilane and two Methyl-monosilane at least any one.

17. film formation devices according to claim 1, it is characterised in that：The reaction for forming the thin layer is only the silicon The oxidation reaction of the utilization oxidizing gas of raw material.

18. film formation devices according to claim 1, it is characterised in that：Form the reaction of the thin layer and then rare Carry out in the presence of gas.

19. film formation devices according to claim 1, it is characterised in that：Possesses controlling organization, it is forming the thin layer Reaction in, to make the quantity delivered of the oxidizing gas not in order that silicon raw material stoichiometry ground completely Aoxidize and required amount.